EP3313569B1 - Procédé de préparation du propylène - Google Patents
Procédé de préparation du propylène Download PDFInfo
- Publication number
- EP3313569B1 EP3313569B1 EP16745522.9A EP16745522A EP3313569B1 EP 3313569 B1 EP3313569 B1 EP 3313569B1 EP 16745522 A EP16745522 A EP 16745522A EP 3313569 B1 EP3313569 B1 EP 3313569B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- mixture
- process according
- propylene
- dehydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims description 82
- 230000008569 process Effects 0.000 title claims description 80
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 51
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 49
- 239000003054 catalyst Substances 0.000 claims description 182
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 88
- 238000005336 cracking Methods 0.000 claims description 69
- 150000001336 alkenes Chemical class 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 58
- 229930195733 hydrocarbon Natural products 0.000 claims description 42
- 150000002430 hydrocarbons Chemical class 0.000 claims description 41
- 238000009835 boiling Methods 0.000 claims description 38
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 239000002808 molecular sieve Substances 0.000 claims description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 230000003111 delayed effect Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 18
- 239000010457 zeolite Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 229910021536 Zeolite Inorganic materials 0.000 description 17
- 239000000571 coke Substances 0.000 description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 238000000605 extraction Methods 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003502 gasoline Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- -1 olefin hydrocarbon compounds Chemical class 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Definitions
- the invention is directed to a process to prepare propylene from a hydrocarbon feedstock comprising olefin hydrocarbon compounds.
- Propylene is for more than 50% produced by steam cracking processes.
- Typical feedstock is straight run naphtha as obtained when refining a crude petroleum source which typically comprises of unsaturated compounds, like paraffinic and naphthenic compounds, and aromatic compounds.
- Steam cracking processes are very complex and for this reason alternative processes starting from naphtha feedstock have been described in US2010/0274063 and US2010/0331590 . These processes involve a dehydrogenation step to increase the olefin compound contents followed by a olefin cracking step wherein propylene is formed.
- Propylene is also prepared in a refinery environment as a by-products of the Fluid catalytic cracking (FCC) process. Since the late nineties, some FCC units have been operating at higher severity to achieve a propylene yield of 10-12 wt percent of the fresh FCC feed. To further increase the propylene yield, different processes have been developed around the FCC configuration in a refinery and it has been reported that propylene yields up to 20 wt% of fresh FCC feed have been achieved.
- FCC Fluid catalytic cracking
- One way to increase the propylene yield is to add a medium pore zeolite to the FCC catalyst as for example described in DE4114874 .
- Various variants have been developed wherein the medium pore catalyst and the FCC catalyst contact the hydrocarbon fractions in riser reactors.
- a development is a FCC process employing two risers as for example described in US2013158326 .
- a disadvantage of these processes is that the medium pore zeolite catalyst will be subjected to a regeneration step together with the FCC catalyst which causes the medium pore zeolite catalyst to degenerate.
- a disadvantage of the dual risers is the complexity of the process and the inflexibility to control the yield of propylene in response to changing economics. This may be the reason that up to this moment very few dual riser FCC units have been build.
- US2012/0071701 describes a process wherein a fraction comprising olefins and paraffins in the C4-C12 range as obtained in a FCC process is first contacted with a olefin conversion reactor. From the effluent of the olefin conversion reactor light olefins, like propylene, are isolated. The remaining fraction is sent to a dehydrogenation reactor. The effluent of the dehydrogenation reactor is recycled to the olefin conversion reactor.
- the olefin conversion reactor and the dehydrogenation reactor may be a fixed bed reactors, fluidized bed reactors or a continuous catalyst regeneration (CCR) system.
- a disadvantage of the process of US2012/0071701 is the high coke formation in the dehydrogenation cracking reactor. This coke formation forces one to perform the dehydrogenation in a fluidised bed reactor applying a separate regeneration reactor resulting in a complex process.
- WO03/082462 describes a process to prepare light olefins by contacting a feedstock with a catalyst having a dehydrogenation function, as provided by a V/Mg metal oxide component, and a cracking function, as provided by a SAPO-34 zeolite.
- the feed was contacted with this catalyst in a fixed bed downflow reactor.
- a fixed bed is favourable the coke make of such a process is relatively high. This will result in that the catalyst will have to be regularly decoked. Furthermore when starting from mixtures of hydrocarbons also containing aromatics more coke forming is to be expected.
- the aim of the present invention is to provide a simpler process for the preparation of propylene starting from a mixture of hydrocarbons comprising aromatic hydrocarbon compounds as may be obtained from a FCC process.
- step (b) when aromatics are partly separated from the hydrocarbon mixture before performing step (b) a more efficient process is obtained. It was also found that when at least 5 wt% of the higher boiling fraction obtained in step (c) is recycled to step (a) the volume of the flow to step (b) in a continuous process is significantly reduced for the same propylene production.
- a further advantage is that the process is performed in packed beds. Even though some regeneration will have to be performed the use of such packed beds, also referred to as fixed beds, greatly simplifies the process when compared to a fluidised bed reactor combined with a fluidised bed regenerator. This process provides for example a simple method to upgrade excess gasoline as produced within a crude oil refinery into much more desired propylene. Especially older refineries being designed for maximum gasoline yield and now faced with a declining gasoline demand could benefit from this invention. Further advantages will be discussed when describing the preferred embodiments.
- the mixture of hydrocarbons used in step (a) may be any mixture of hydrocarbons comprising paraffins, olefins, naphthenic and aromatic compounds.
- the feedstock is a mixture of these hydrocarbons boiling for more than 90 wt% between 35 and 250 °C.
- the content of olefins having 4 or more carbon atoms in the feedstock is suitably between 1 and 100 wt%, preferably between 1 and 70 wt% and even more preferably between 1 and 50 wt% and most preferred between 1 and 20 wt%.
- Feedstock having a high olefin content, suitably higher than 5 wt%, are especially suitable to be converted by the process according to this invention to propylene.
- the feedstock may for example be any fraction as obtainable in a crude oil refinery having the above properties.
- Suitable feedstock may comprise a light straight run naphtha.
- Light Straight Run naphtha is a preferred feedstock because it is an extremely poor component to be directly used as part of a gasoline product.
- the Light Straight Run naphtha typically requires severe processing in a Catalytic Reforming Unit which is not advantageous because this will limit the cycle length of said Catalytic Reformer.
- Other refinery fractions, boiling in the above referred to range, suited to be used a feedstock or part of the feedstock are fractions as isolated from the effluent of a hydrogen depletion process, such as delayed cocker process and the fluid catalytic cracking process.
- a preferred feedstock are the fractions rich in hydrogen as isolated from the effluent of hydrotreating or hydrocracking processes. Another suitable fraction may be isolated from the effluent of a Catalytic Polymerisation Process. Other possible feedstock may comprise natural gas liquids, any other fraction boiling as described above and isolated from a refinery or chemical process. Even fractions as obtained from sources such as Fischer Tropsch synthesis, lube oil extracts, waxes or other hydrocarbon feeds boiling in the above referred to range may be contemplated.
- Suitable refinery fractions are those isolated from the effluent of a fluid catalytic cracking (FCC) process are used as the feedstock or as part of the feedstock.
- FCC fluid catalytic cracking
- Such a FCC unit may be operated with propylene enhancing additional catalysts, like the medium pore zeolite catalysts.
- the applicant has found that by using the process of this invention such use may be omitted and still prepare propylene in a high yield as calculated on fresh FCC feedstock. This is advantageous because less or no medium pore size zeolite is required to be supplied to the FCC process as replacement for degraded catalyst.
- the feedstock may be comprised of mixtures of this fraction and other fractions as described above.
- the feedstock will for its majority be comprised of the above hydrocarbons. Small amounts of for example water, sulphur compounds, nitrogen compounds may be present.
- the content of hydrocarbons in the feedstock will be above 95 wt%, suitably above 98 wt%.
- the above mixture of hydrocarbons may be blended with pentane and iso-pentane as isolated from gasoline fractions in a refinery environment. It has been found to be desired to separate pentane and iso-pentane from these gasoline fractions in order to obtain a gasoline blending stock which is suited to meet the Reid vapor pressure (RVP) specification of motor fuels.
- RVP Reid vapor pressure
- Step (a) is important in the process according to the invention.
- Aromatics as present in the feed and present in the recycle stream are substantially inert in step (b).
- Aromatics have the effect of diluting reactants and increasing recycle stream rates.
- Applicants have also investigated what would be the build up of aromatics when the aromatic extraction would be performed after performing step (c).
- the feed to the reactor containing the cracking catalyst in step (b) would be in tons/hour: Extraction according to invention 26782 No Extraction 72214 Post Extraction 44187
- step (d) part of the higher boiling fraction is recycled to step (b) and at least 5 wt% of the higher boiling fraction is recycled to step (a).
- step (a) compounds such as benzene, toluene, xylene and para-xylene are separated from the mixture of hydrocarbons and recycle.
- benzene, toluene, xylene and para-xylene are separated from the mixture of hydrocarbons and recycle.
- more than 90 wt% of the combined benzene, toluene and xylene are extracted from the total feed to step (a) in step (a).
- suitable extraction solvents are diethylene glycol, tetraethylene glycol, diethylene glycol, dimethyl sulfoxide, sulfolane, N-formyl morpholine, N-methyl pyrrolidone, a glycol-glycol ether mixture and tertrahydrothiophene 1-1 dioxide.
- an aromatic extraction process is preferred which is selective for aromatics in the presence of olefins.
- a suitable extraction process is an extractive distillation using one of the aforementioned solvents and suitably sulfolane, N-formyl morpholine or N-methyl pyrrolidone, optionally in combination with a suitable co-solvent.
- a suitable commercially available process is the so-called GT-BTX PluS type as developed and offered by GTC Technology, Houston Texas.
- the heterogeneous cracking catalyst may suitably comprise an acidic material. Suitable acidic materials are those which can crack the gasoline range olefins to propylene. Such an acidic material may be a molecular sieve or a material having strong acid sites.
- a first type of heterogeneous cracking catalyst does not comprise a molecular sieve and does comprise a material having strong acid sites as the acidic material.
- a suitable acidic material is an amorphous or semi-crystalline material chosen from the group of heteropoly acids, alumina, boehmite alumina, gamma alumina, theta alumina, silica alumina, silica-titania, silica-tungsten, silica phosphorous, silica-alumina-phosphorous.
- the acidic material may also be a molecular sieve.
- An advantage of a molecular sieve is the high acid site density per reactor volume.
- various molecular sieves increase hydrogen transfer and limit the propylene yield in this process.
- a choice regarding the most suited acidic material shall have to be made.
- an optional carrier as part of the catalyst particles may have no strong acid sites, some strong acid sites or only strong acids sites.
- suitable optional carrier will depend on the composition of the feedstock. Preferably the carrier does not have strong acid sites.
- the molecular sieve may have 8-membered oxygen ring channels such as Chabazite, also referred to as CHA structure type according to the Atlas of zeolite structure types, 4 th rev. ed/W.M.Meier, D.H.Olson and Ch.Baerlocher.
- a typical example of such a molecular sieve is SAPO-34.
- the molecular sieve is suitably an intermediate pore-size zeolite.
- intermediate pore-size zeolite is meant to indicate any zeolite of which the pore size is intermediate between the pore size of a small pore-size zeolite such as typically A-type zeolite, and the pore size of a large pore-size zeolite such as typically mordenite, or X-type or Y-type zeolite".
- the intermediate pore size zeolite has a 10 or 12-membered oxygen ring in the crystal structure thereof.
- the zeolite suitably has a silica to alumina ratio between 10-300 and more preferred between 10-50.
- Examples of the intermediate pore-size zeolite are ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-21, ZSM-23, ZSM-35, ZSM-38.
- the molecular sieve is chosen from the structure types having a 10-ring channels according to structure types MFI, MEL, IMF, TUN and EUO.
- MFI is also known as ZSM-5
- MEL is known as ZSM-11
- IMF is known as IM-5
- TUN is known as TNU-9.
- MFI is most preferred in view of its availability combined with its performance.
- the above molecular sieves may be present as such to provide the cracking catalyst.
- the molecular sieve is comprised in a carrier, wherein the weight content of the molecular sieve in the heterogeneous catalyst is between 5 and 70 wt%.
- the carrier may be silica, silica-alumina or alumina and may be suitably treated with phosphorous.
- the invention is also directed to a process wherein next to propylene also butylene is isolated from the reaction products.
- the heterogeneous cracking catalyst suitably comprises a 12 member oxygen ring zeolites as the acidic material, preferably zeolite beta (BEA) and mordenite (MOR) are preferred.
- the acidic material may also be an amorphous or semi-crystalline acidic material such as alumina, boehmite alumina, silica-alumina, silica phosphate alumina, silica doped with phosphorous and silica doped with tungsten.
- the cracking catalyst may be present in the fixed bed as discrete particles preferably having a volume mean diameter of between typically 1 mm to 3 cm.
- the process is performed by contacting the mixture as obtained in step (b) in with a heterogeneous dehydrogenation catalyst in a step (b1) as present in a fixed bed.
- the effluent of step (b1) is the cracked effluent from which propylene is separated in step (c).
- step (b) is performed by contacting the mixture obtained in step (a) with a mixture of a heterogeneous cracking catalyst and a heterogeneous dehydrogenation catalyst as present in one or more packed beds thereby obtaining propylene and other reaction products.
- the cracking catalyst and the dehydrogenation catalyst may for example be comprised in one particle as for example described in WO03/082462 and have a volume mean diameter of between 1 mm and 3 cm.
- the cracking catalyst and the dehydrogenation catalyst are present in one or more packed beds in an in-series configuration and wherein the hydrocarbon feedstock, formed propylene and other reaction products will flow from an up-flow region to a down-flow region following a flow path and wherein in the direction of the flow path the concentration of the dehydrogenation catalyst in the bed increases compared to the cracking catalyst.
- the mixture obtained in step (a) is contacted as described less coking is found to occur as compared to when the process is performed by contacting with a homogenously mixed dehydrogenation and cracking catalyst or when the cracking catalyst and dehydrogenation catalyst are present in separate beds or reactors.
- the cracking catalyst and the dehydrogenation catalyst are present in one or more packed beds in an in-series configuration.
- this packed bed or beds the hydrocarbon feedstock, formed propylene and other reaction products will flow from an up-flow region to a down-flow region following a flow path.
- the packed bed or packed beds in series will comprise such a flow path.
- the flow path runs from the first catalyst packed bed, the most up-flow catalyst bed, up to the last catalyst packed bed, the most down flow catalyst bed.
- the flow path may also consist of more than 80% or even more preferably more than 90% of such a maximum flow path length.
- these compounds flow in a plug flow or semi-plug flow fashion through the packed bed or beds.
- the configuration of the packed beds is preferably so chosen that such back-mixing is avoided as much as possible.
- the dehydrogenation catalyst and the cracking catalyst are present in the same ratio throughout the entire bed or beds or said otherwise along the entire flow path. This ratio may vary along the flow path.
- the concentration of the dehydrogenation catalyst in the bed increases compared to the cracking catalyst.
- the feedstock comprises relatively more olefins than paraffins, preferably wherein the weight ratio olefins to paraffins is greater than 0.75:1.
- relatively more cracking catalyst will be present in the up-flow region and relatively more dehydrogenation catalyst will be present in the down-flow region.
- the lower coke make in such a packed bed or beds is lower because the local concentration of higher olefins, i.e. olefins having more than 6 carbon atoms, can be kept low.
- the cracking catalyst is present along the entire length of the flow path while the content of the dehydrogenation catalyst relative to the total content of heterogeneous catalyst particles as present in the packed bed or beds increases along the flow path length in the direction of the flow.
- the content of dehydrogenation catalyst may be zero at the start of the flow path and for example gradually or step-wise increase along the flow path length.
- the cracking catalyst and dehydrogenation catalyst are suitably separate particles each having a chosen composition and size. This simplifies the catalyst loading of the packed bed or beds. But the cracking catalyst and/or dehydrogenation catalyst may also have a variable composition along the length of the flow path.
- the cracking catalyst and dehydrogenation catalyst may even be comprised in one particle which composition varies along the length of the flow path such to achieve the above described desired ratio between the cracking catalyst or better said cracking catalyst functionality and the dehydrogenation catalyst or better said the dehydrogenation functionality.
- the content of the dehydrogenation catalyst particles may vary along the path way as described below.
- the content in volume percent of the dehydrogenation catalyst particles relative to the total volume of catalyst particles suitably varies from between 0 and 100% at the start of the flow path more preferred between 1 and 100, more preferred between 5 and 100, more preferred between 20 and 100, to between 0 and 100% at the end of the flow path, more preferred between 5 and 95%, more preferred between 10 and 90, more preferred between 20 and 80%.
- the content in volume percent of the dehydrogenation catalyst particles relative to the total volume of catalyst particles varies from between 0 and 50 % at the start of the flow path to between 20 and 80% at the end of the flow path. More preferably in process (ii) the content in volume percent of the cracking catalyst particles relative to the total volume of catalyst particles varies from between 5 and 50 % at the start of the flow path to between 20 and 100% at the end of the flow path.
- the start of the flow path is defined as the first 20% of the length of the flow path.
- the end of the flow path is defined as the last 20% of the length of the flow path.
- dehydrogenation catalyst The most preferred contents of dehydrogenation catalyst will depend on the chosen cracking catalyst and dehydrogenation catalyst and their catalytic activity at the conditions at which the hydrocarbon feedstock is contacted with the catalysts. Such optimal conditions may be found by simple trial and error by the skilled person.
- the separate or combined cracking catalyst and/or dehydrogenation catalyst particles have a varying composition and/or size along the length of the flow path the above optimal contents of the dehydrogenation catalyst will obviously be different.
- the heterogeneous cracking and heterogeneous dehydrogenation catalyst other catalytically or non-catalytically active particles may be present in the one or more packed beds.
- the heterogeneous cracking catalyst and the dehydrogenation catalyst may also be present as a structured packing. Both the catalyst types may be incorporated in one structured packing. If a gradient is desired as described above different blocks of structured packing may be used wherein the blocks have a varying ratio of the two catalyst types. By placing the blocks in a certain order the desired gradient may be obtained. Alternatively blocks may be used wherein one type of block comprises the cracking catalyst and another type of block comprises the dehydrogenation catalyst. By placing the blocks in a certain order and alternating the types a homogeneous mixture of both catalyst types according the invention is obtained. In such an embodiment the total number of blocks or zones along the flow path is preferably above 1, preferably above 5 and more preferably above 10.
- the flow path length of the alternating blocks of cracking catalyst and dehydrogenation catalyst may be varied.
- the total flow path length of the cracking catalyst structured packing may be longer in the first half of the flow path length and shorter in the second half of the flow path length relative to the flow path length through the dehydrogenation structured packing.
- the dehydrogenation catalyst suitably comprises a transition metal or a noble metal, one or more additive components and a carrier.
- the transition and noble metals are defined as any element in the d-block of the periodic table, which includes groups 3 to 12 on the periodic table.
- suitable metals exhibiting dehydrogenation properties are especially Cr and Pt, though other metals such as Mn, Zn, Co, Cu, Ni, or mixtures of these can be used as well. It is known in the art to increase the stability of Pt with Sn to lower the deactivation by coke, and alkaline metals on support can improve the selectivity by strong metal support interaction.
- Suitable additive components are Sn, Ga, alkaline metal, alkaline earth metal or combinations.
- suitable carrier materials are alumina, silica-alumina, silica, Kaolin, anionic clay, spinel, diatomite.
- a suitable dehydrogenation catalyst may be a zirconia-based catalyst comprising zirconia in an amount of at least 40 wt%, suitably between 50 and 90 wt%.
- the catalyst may also comprise other metal oxides as the additive component, for example oxides of one or more metals selected from the group consisting of scandium, yttrium, lanthanum, cerium, actinium, calcium and/or magnesium. If used, the metal oxide(s) other than zirconia is/are generally present in an amount of at most 10 percent by weight of the dehydrogenation catalyst.
- the catalyst may further comprise suitable carriers as described above incorporated into the catalyst in a total amount of generally at most 50 percent by weight of the dehydrogenation catalyst.
- the dehydrogenation catalyst may also be a so-called oxydehydrogenation catalysts as described in WO03/082462 or US5530171 wherein next to the above transition metal the dehydrogenation catalyst comprises a solid oxygen source comprising a reducible metal oxide, such as for example a reducible metal oxide of at least a transition metal selected, suitably Bi, In, Sb, Zn, TI, Pd and Te.
- a reducible metal oxide such as for example a reducible metal oxide of at least a transition metal selected, suitably Bi, In, Sb, Zn, TI, Pd and Te.
- Possible solid oxygen carriers are CeO 2 , doped cerium oxides and preferably Bi 2 O 3 .
- the solid oxygen source may also be part of a further separate catalyst particle as present in the packed bed or beds.
- the presence of a oxydehydrogenation catalyst is advantageous because it helps to drive the dehydrogenation reaction to completion and prevents the reverse reaction, the hydrogenation of olefins by the presence
- the dehydrogenation catalyst may be present in the fixed bed as discrete particles preferably having a volume mean diameter of between typically 1 mm to 3 cm.
- the overall ratio between the cracking catalyst and the dehydrogenation catalyst will depend on their relative activities.
- the relative rate of cracking over the cracking catalyst should preferably outpace the olefin generation over the dehydrogenation catalyst to limit the coke generation.
- the removal rate of large olefins exceeds the generation rate of these at every stage in the bed.
- cracking rates and dehydrogenation rates depend on the local composition of the reaction mixture in the packed bed, their concentration (partial pressure), hydrogen partial pressure and temperature, these numbers can be obtained empirically or using kinetics obtained over the respective cracking catalyst and dehydrogenation catalyst.
- olefins especially C7-C12 olefins
- C7-C12 olefins are found to rapidly crack to for example propylene when contacted with a ZSM-5 based cracking catalyst.
- C16 olefins and especially normal-olefins, are found to easily crack.
- paraffinic waxes can be a prime feedstock to crack over ZSM-5. Though smaller C3-C6 range paraffins will not readily crack.
- the paraffins are first converted to olefins over the dehydrogenation catalyst.
- To optimize the reactivity of the feedstock a balance has to be struck between cracking of olefins versus the generation of olefins from non-olefinic components, i.e.
- paraffins This balance will be a dependent on the feedstock and differ from the inlet to the outlet as the feed composition along the flow path will be different.
- the olefins will crack first and form light olefins.
- the composition of paraffins will change throughout the reactor as the paraffins that most readily dehydrogenate will do so after short residence time in the bed, relatively shortly after entering the reactor.
- the more stable paraffins will only be converted into olefins farther in the bed, or in some cases not at all. Therefore the optimal concentration profile for dehydrogenation catalyst and cracking catalyst will depend strongly on the composition of the feedstock.
- the process conditions may vary as a result of the combination of cracking catalyst and dehydrogenation catalyst.
- the temperature is between 300C and 750 °C, more preferred between 400 and 650 °C, most preferred between 450 and 600 °C.
- the absolute pressure is suitably between 0.05 and 10 MPa and preferably between 0.1 and 0.5 MPa. It is preferred to reduce residence time, suppress coke make and reduce hydrocarbon partial pressure via dilution of steam. The reduction in hydrocarbon partial pressure boosts the dehydrogenation reaction, suppresses the reverse reaction, and suppresses the recombination of light olefins.
- the Weight hourly space velocity, WHSV, as expressed in mass flow (per hour) divided by the mass of the catalyst is preferably higher than 20/hour and more preferably higher than and including 50/hour. Applicants found that by increasing the WHSV even more the olefin yield remains high while allowing the use of smaller reactor vessels. So for this reason a WHSV of above 100/hour is most preferred. This allows in use a lower feed rate than the design feed rate and still maintaining a high olefin yield.
- the feed is the hydrocarbon feed and any optional diluents, eg inert diluents. For example, a 30% dilution with nitrogen results in an increase of 30% in WHSV.
- the process is carried out in one or more packed beds.
- more than one bed is here meant any packed beds which are arranged in series with respect to each other.
- a similar second or even a third set of packed bed or beds may be arranged parallel to said first bed or beds.
- These second or third bed or beds may be used for performing the process according to the invention when the first bed or beds are regenerated to remove coke and optionally other contaminants.
- An example of such a regeneration process is when the reactors are operated as a simulated moving bed. It is also conceivable that not all packed beds in one set of beds in series are regenerated at a time. Instead a packed bed in a set of packed beds may have a longer run time as a result of the different catalyst composition with the packed bed and thus require less frequent regeneration than the remaining beds in the same in-series configuration.
- the process may be advantageous to remove some of the low boiling reaction products including propylene from the reaction mixture in between the packed beds. This may be performed by means of a flash separation.
- the low boiling gasses thus obtained may be provided to a separation unit in which propylene is isolated from the reaction products of the most down-stream packed bed as will be described in more detail below.
- the higher boiling fraction as obtained in such a separation may be provided to the next bed or even internally recirculated to one or more of the up stream beds, optionally after reheating this fraction.
- the chosen recycle will depend on the olefin content in such a higher boiling fraction and the catalyst gradient in the packed beds.
- the content of the dehydrogenation catalyst relative to the total content of heterogeneous catalyst particles increases in the direction of the flow it may be advantageous to recycle to the more upstream beds when the olefin content is high.
- Such a direct recycle may also be performed with the higher boiling fraction as obtained when low boiling gasses are separated from the final effluent of the one or more packed beds.
- the cracking catalyst and the dehydrogenation catalyst may also be present in one packed bed.
- the propylene and optionaly the butylenes as formed in the process is/are suitably isolated from the effluent as discharged from the packed bed or beds from higher boiling compounds and wherein all or part of these higher boiling compounds are recycled to the packed bed or beds.
- propylene and optionally the butylenes will also be separated from other low and lower boiling compounds, such as for example ethane, ethylene, hydrogen and any water.
- Such a separation may include distillation and/or flash separation. It is found that almost no propane is formed in a great amount in the process. This is advantageous because this results in that no difficult propylene and propane separation is required to obtain a polymer grade propylene.
- ethylene as a valuable by-product may be isolated from the low boiling compounds.
- the C4 fraction including butane and butylene may be recovered as such or be recycled together with the higher boiling compounds to the packed bed or beds.
- the higher boiling compounds as obtained in this separation comprises for more than 90 wt% of hydrocarbons boiling above 75 °C.
- Any low boiling fractions separated from intermediate streams between the packed beds as described above may be fed to this separation.
- Such a fraction may contain some high boiling compounds because of the coarse separation and by feeding this fraction to this separation these high boiling compounds are recovered to be recycled to the packed bed or beds.
- the hydrocarbon feedstock comprising olefin hydrocarbon as used in the process according to the invention has an aromatics content, i.e. a benzene, toluene and xylene content, of below 50 wt%, preferably below 20 wt% and even more preferably below 10 wt%.
- This aromatics content relates to the feedstock as being fed to the packed bed or beds and thus includes the so-called fresh feedstock optionally combined with the above referred to recycle of higher boiling compounds after these fractions have been subjected to the aromatic extraction step.
- Figure 1 shows a process scheme for a process to prepare propylene according to one embodiment of the present invention.
- a hydrocarbon fraction boiling between 35 and 250 °C is mixed with a recycle stream 2 to obtain a combined stream 3.
- Combined stream 3 is fed to an aromatics extraction unit 4 in which benzene, toluene and xylene are extracted from the mixture of hydrocarbons thereby obtaining a mixture of hydrocarbons poor in aromatics in stream 5 and a stream 4 comprising these aromatic compounds.
- the mixture of hydrocarbons poor in aromatics in stream 5 is mixed with a second recycle stream 6 to obtain a feedstock stream 8.
- the composition of recycle stream 2 and recycle stream 6 are the same in the process of this Figure.
- the mass flow of stream 2 and 6 may be different such that stream 2 is at least 5 wt% of the combined streams 2 and 6 (stream 7) and preferably between 10 and 30 wt% of the combined streams 2 and 6 (stream 7).
- Feedstock stream 8 is raised in temperature in an indirect heat exchanger 9 against hot reactor effluent stream 10.
- the partly heated feedstock stream 8 is further increased in temperature in furnace 11 before being fed to the up-flow region 12 of the flow path as present in packed bed reactor 13.
- the flow path will run from the up-flow region 12 to the down-flow region 15 in packed bed 14.
- the furnace 11 may use for example fuel gas or fuel oil as fuel.
- Part of the feedstock stream may be fed via stream 22 to an intermediate position in the flow path. This may be advantageous when the content of the dehydrogenation catalyst relative to the total content of heterogeneous catalyst particles increases in the direction of the flow. In such a configuration a feedstock stream 8 containing relatively low amounts of olefins may advantageously be recycled to an intermediate section of reactor 13 via stream 22.
- the up-flow region 12 of the catalyst bed will be primarily or exclusively cracking catalysts which will convert higher molecular weight olefins into propylene & butylene.
- the resulting olefin lean hydrocarbon mixture will then begin to contact more dehydrogenation catalyst in the reactor bed in the more down-flow regions 15.
- the paraffinic components of this mixture will be converted to high molecular weight olefins.
- the rapid conversion of the high molecular weight olefins into low molecular weight olefins results in a significantly reduced coking tendency within the catalyst bed. This coking is a result of the interaction of the high molecular weight olefins with the dehydrogenation catalyst surface.
- the packed bed 14 may also comprise a solid oxygen source catalyst.
- the solid oxygen source catalyst will supply oxygen which in turn reacts with the formed hydrogen to water. Removal of the high molecular weight olefins and removal of hydrogen pushes the equilibrium dehydrogenation reaction in favour of more olefin production.
- the oxygen in the oxidation catalyst lattice will be recharged during the regeneration step.
- the cracked effluent as being discharged from packed bed reactor 13 in stream 10 will comprise the desired propylene and ethylene, butylene and a higher boiling fraction comprising non-reacted feed stock and small amounts of aromatic by-products.
- the cracked effluent in stream 10 is reduced in temperature in indirect heat exchanger 9, air coolers 16 and chilled water trim coolers 17. Other methods of cooling are also possible.
- Propylene in stream 19 and optionally other valuable lower olefins may be separated from the cracked effluent in a single stage flash separation 18.
- propylene and other olefins may be separated from the cracked effluent by means of one or more distillation columns or any other process sufficient to separate the light olefin product from the cracked effluent.
- a part may be discharged as a purge via stream 21 to avoid a build-up of inert materials in the recycle stream.
- the remaining higher boiling fraction in stream 7 may be recycled to the aromatics extraction unit 3 and directly to the packed bed reactor 13 as described above.
- part of the stream 7 may be recycled via stream 23 to an intermediate position in the flow path in packed bed reactor 13. This may be advantageous when the content of the dehydrogenation catalyst relative to the total content of heterogeneous catalyst particles increases in the direction of the flow.
- a recycle stream containing relatively low amounts of olefins may advantageously be recycled to an intermediate section of reactor 13 via stream 23.
- the recycle stream 23 is preferably heated in a heater(not shown), like a heat exchanger and/or furnace. This configuration provides the operator of the process to optimise the recycle streams 2, 6 and 23 depending for example on the composition of stream 7.
- One of the key discoveries of this present invention is the gradient of cracking catalysts mixed with the dehydrogenation catalysts which converts the coke precursors, i.e. the high molecular weight olefins, into ethylene, propylene & butylene before conversion to coke. Nevertheless, the packed beds of catalysts will require regeneration to burn the coke in the presence of oxygen into CO 2 .
- a second reactor will be on stand-by for operation when the first reactor requires regeneration. The reactor just taken out of service will then be regenerated in preparation for its next cycle when the present reactor requires regeneration. This process will thereby continue without interruption.
- a packed bed reactor consisting of a mixture of a dehydrogenation catalyst and a cracking catalyst.
- the dehydrogenation catalyst was a typical platinum tin supported on alumina dehydrogenation catalyst.
- the cracking catalyst contained 50 wt% ZSM-5 in a silica-alumina-phosphate support. The content of dehydrogenation catalyst gradually increases from 0% at the start of the flow path for a hydrocarbon feed to 50 wt.% at the end of the flow path.
- a packed bed reactor having a single layer consisting of a 1:1 wt%/wt% mixture dehydrogenation catalyst and cracking catalyst.
- the dehydrogenation catalyst and cracking catalyst are the same as in Example 1.
- the total volume of the single catalyst layer was the same as the total volume of catalysts present in the reactor of Example 1.
- the FCC full range naphtha of Example 1 was fed to the reactor at a 0.25 g/min in 50 ml/min nitrogen via the flow path at 500 and 550 °C.
- the pressure in the reactor was 0.048 MPag (7 psig).
- the effluent was analysed and the results are provided in Table 1.
- Table 1 50:50 Blend Gradient Example 2
- Example 1 Temperature 500 550 500 550 H2 + C1 + C2 0.9 2.0 0.6 1.7 C3 2.0 2.5 2.3 2.9
- a packed bed reactor having a first layer of cracking catalyst and a second layer of dehydrogenation catalyst.
- the dehydrogenation catalyst and cracking catalyst are the same as in Example 1.
- the total volume of the two catalyst layers was the same as the total volume of catalysts present in the reactor of Example 1.
- a flow path for a hydrocarbon feed runs from the first layer to the second layer.
- the FCC full range naphtha of Example 1 was fed to the reactor at 0.25 g/min in 50 ml STP/min nitrogen via the flow path at 500 and 550 °C.
- the pressure in the reactor was 0.048 MPag (7 psig).
- the effluent was analysed and the results are provided in Table 2.
- Table 2 show an improved yield for propylene in combination with a gasoline by-product which has substantially lower contents iso-pentane and pentane (part of the gasoline) which is beneficial for the Reid vapor pressure and the motor octane yield.
- a mass balance is calculated for the process of Figure 1 .
- FCC naphtha having a composition of 35.3 wt% olefins, 38.7 wt% paraffins, 8.5 wt% naphthenes and 17.5 wt% aromatics is provided to the process as stream 1.
- Reactor 13 has a packed bed as composed as in Example 1.
- Table 6 the mass balance is provided for a situation wherein 20 wt% of stream 7 is recycled to aromatics extraction column 3 via 2 and 80wt% of stream 7 is recycled directly to reactor 13 via stream 6.
- Propylene 25 Recycle 99 10 89 BTX total of benzene, toluene and xylene
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Claims (15)
- Procédé pour préparer du propylène à partir d'un mélange d'hydrocarbures par réalisation des étapes suivantes :(a) extraction d'aromatiques à partir du mélange d'hydrocarbures, permettant ainsi d'obtenir un mélange d'hydrocarbures pauvre en aromatiques ;(b) mettre en contact le mélange obtenu à l'étape (a) avec un catalyseur de craquage hétérogène tel que présent dans un lit fixe, permettant ainsi d'obtenir un effluent craqué ;(c) séparer le propylène de l'effluent craqué, permettant ainsi également d'obtenir une fraction à point d'ébullition élevé ;(d) recycler une partie de la fraction à point d'ébullition élevé à l'étape (b) et au moins 5 % en poids de la fraction à point d'ébullition élevé à l'étape (a).
- Procédé selon la revendication 1, dans lequel, à l'étape (d), entre 10 et 30 % en poids de la fraction à point d'ébullition élevé sont recyclés à l'étape (a) .
- Procédé selon la revendication 1, dans lequel le mélange d'hydrocarbures comprend entre 1 et 70 % en poids d'oléfines ayant au moins 4 atomes de carbone.
- Procédé selon la revendication 3, dans lequel le mélange d'hydrocarbures comprend entre 1 et 20 % en poids d'oléfines ayant au moins 4 atomes de carbone.
- Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le mélange d'hydrocarbures est un mélange de paraffines, d'oléfines, de composés naphténiques et aromatiques bouillant pour plus de 90 % en poids entre 35 et 250°C.
- Procédé selon la revendication 5, dans lequel le mélange d'hydrocarbures comprend un naphta léger de distillation directe et/ou une fraction telle qu'isolée à partir de l'effluent de l'un quelconque des procédés suivants comprenant le craquage catalytique en lit fluide, la polymérisation catalytique, l'hydrotraitement, l'hydrocraquage et/ou la cokéfaction retardée.
- Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le mélange obtenu à l'étape (b) est mis en contact dans une étape (b1) avec un catalyseur de déshydrogénation hétérogène tel que présent dans un lit fixe et dans lequel l'effluent de l'étape (b1) est l'effluent craqué à partir duquel du propylène est séparé à l'étape (c).
- Procédé selon l'une quelconque des revendications 1 à 6, dans lequel l'étape (b) est effectuée par mise en contact du mélange obtenu à l'étape (a) avec un mélange d'un catalyseur de craquage hétérogène et un catalyseur de déshydrogénation hétérogène tel que présent dans un ou plusieurs lits à garnissage, permettant ainsi d'obtenir du propylène et autres produits de réaction, le catalyseur de craquage et le catalyseur de déshydrogénation étant présents dans au moins un lit à garnissage dans une configuration en série, et dans lequel la charge d'alimentation hydrocarbonée, le propylène formé et les autres produits de réaction s'écouleront d'une région à écoulement ascendant à une région à écoulement descendant suivant un trajet d'écoulement, et dans lequel, dans la direction du trajet d'écoulement, la concentration du catalyseur de déshydrogénation dans le lit augmente par comparaison avec le catalyseur de craquage.
- Procédé selon la revendication 8, dans lequel le catalyseur de craquage et le catalyseur de déshydrogénation sont présents dans le ou les lits à garnissage en tant que particules séparées et dans lequel la teneur en pourcentage en volume des particules de catalyseur de déshydrogénation par rapport au volume total de particules de catalyseur varie d'entre 0 et 50 % au début du trajet d'écoulement à entre 20 et 100 % à la fin du trajet d'écoulement.
- Procédé selon l'une quelconque des revendications 1 à 9, dans lequel la température à l'étape (b) est entre 300 et 750°C, de façon davantage préférée entre 300 et 700°C, de la façon que l'on préfère le plus entre 450 et 600°C et la pression absolue est de façon appropriée entre 0,1 et 10 MPa, de façon davantage préférée entre 0,1 et 0,5 MPa, et dans lequel la vitesse spatiale horaire pondérale (WHSV) est supérieure à et y compris 50/heure et, de façon encore plus préférée, supérieure à 100/heure.
- Procédé selon l'une quelconque des revendications 8 à 10, dans lequel la charge d'alimentation est en contact avec le mélange d'un catalyseur de craquage hétérogène et d'un catalyseur de déshydrogénation hétérogène en présence de vapeur d'eau de dilution.
- Procédé selon l'une quelconque des revendications 1 à 11, dans lequel le catalyseur de craquage hétérogène comprend une matière acide qui est un tamis moléculaire.
- Procédé selon la revendication 12, dans lequel le tamis moléculaire est choisi parmi les types de structure BEA, CHA, MOR, MFI, MEL, IMF et/ou TUN.
- Procédé selon l'une quelconque des revendications 8 à 13, dans lequel le catalyseur de déshydrogénation est un catalyseur d'oxydéshydrogénation et/ou par le fait que le ou les lits à garnissage comprennent des particules séparées de catalyseur source d'oxygène solide.
- Procédé selon l'une quelconque des revendications 1 à 14, dans lequel le mélange obtenu à l'étape (a) a une teneur en aromatiques de moins de 20 % en poids.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL2015016A NL2015016B1 (en) | 2015-06-23 | 2015-06-23 | Process to prepare propylene. |
PCT/NL2016/050444 WO2016209074A1 (fr) | 2015-06-23 | 2016-06-23 | Procédé de préparation de propylène |
Publications (2)
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EP16745522.9A Active EP3313569B1 (fr) | 2015-06-23 | 2016-06-23 | Procédé de préparation du propylène |
EP16745521.1A Active EP3313568B1 (fr) | 2015-06-23 | 2016-06-23 | Procédé de préparation du propylène |
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US (2) | US10479740B2 (fr) |
EP (2) | EP3313569B1 (fr) |
KR (1) | KR20180034398A (fr) |
NL (1) | NL2015016B1 (fr) |
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NL2018256B1 (en) | 2016-12-21 | 2018-06-28 | Inovacat B V | Process to prepare propylene |
WO2018117820A1 (fr) * | 2016-12-21 | 2018-06-28 | Inovacat B.V. | Procédé de préparation de propylène |
CN110982552A (zh) * | 2019-12-06 | 2020-04-10 | 贺兰增 | 一种加氢反应器、加氢反应装置及催化加氢工艺 |
EP4081617A4 (fr) | 2019-12-23 | 2024-01-03 | Chevron U.S.A. Inc. | Économie circulaire de déchets plastiques en polypropylène et huile lubrifiante par l'intermédiaire d'unités fcc de raffinerie et de déparaffinage par isomérisation |
KR102503324B1 (ko) | 2021-12-02 | 2023-02-28 | 주식회사 나노 | 탈질-산화 복합 촉매 구조체 및 그 제조방법 |
US11840505B1 (en) * | 2022-09-07 | 2023-12-12 | Saudi Arabian Oil Company | Process and cracking catalyst for cracking butenes to produce light olefins |
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US2331427A (en) * | 1939-06-28 | 1943-10-12 | Phillips Petroleum Co | Control of catalytic reactions |
US2322366A (en) * | 1939-11-29 | 1943-06-22 | Universal Oil Prod Co | Hydrocarbon conversion process |
US3714022A (en) * | 1970-09-22 | 1973-01-30 | Universal Oil Prod Co | High octane gasoline production |
US4835127A (en) * | 1983-11-16 | 1989-05-30 | Phillips Petroleum Company | Oxidative dehydrogenation and cracking of paraffins using a promoted cobalt catalyst |
FR2663946B1 (fr) | 1990-05-09 | 1994-04-29 | Inst Francais Du Petrole | Procede de craquage catalytique en presence d'un catalyseur renfermant une zeolite zsm a ouverture de pore intermediaire. |
US5530171A (en) | 1993-08-27 | 1996-06-25 | Mobil Oil Corporation | Process for the catalytic dehydrogenation of alkanes to alkenes with simultaneous combustion of hydrogen |
US7145051B2 (en) * | 2002-03-22 | 2006-12-05 | Exxonmobil Chemical Patents Inc. | Combined oxydehydrogenation and cracking catalyst for production of olefins |
US6867341B1 (en) * | 2002-09-17 | 2005-03-15 | Uop Llc | Catalytic naphtha cracking catalyst and process |
CN101348409B (zh) | 2007-07-19 | 2011-06-15 | 中国石油化工股份有限公司 | 一种生产低碳烯烃的方法 |
US20100331590A1 (en) * | 2009-06-25 | 2010-12-30 | Debarshi Majumder | Production of light olefins and aromatics |
US9150465B2 (en) | 2010-09-21 | 2015-10-06 | Uop Llc | Integration of cyclic dehydrogenation process with FCC for dehydrogenation of refinery paraffins |
BR112013012925B1 (pt) * | 2010-11-25 | 2018-08-21 | Sk Innovation Co., Ltd. | Método de produção de produtos aromáticos e produtos olefínicos a partir de uma fração de petróleo contendo composto aromático |
US9238600B2 (en) | 2011-12-14 | 2016-01-19 | Uop Llc | Dual riser catalytic cracker for increased light olefin yield |
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- 2016-06-23 WO PCT/NL2016/050444 patent/WO2016209074A1/fr active Application Filing
- 2016-06-23 US US15/737,830 patent/US10479740B2/en active Active
- 2016-06-23 WO PCT/NL2016/050443 patent/WO2016209073A1/fr active Application Filing
- 2016-06-23 KR KR1020187001503A patent/KR20180034398A/ko not_active Application Discontinuation
- 2016-06-23 EP EP16745522.9A patent/EP3313569B1/fr active Active
- 2016-06-23 US US15/737,824 patent/US10919820B2/en active Active
- 2016-06-23 EP EP16745521.1A patent/EP3313568B1/fr active Active
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Also Published As
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WO2016209073A1 (fr) | 2016-12-29 |
US10479740B2 (en) | 2019-11-19 |
EP3313569A1 (fr) | 2018-05-02 |
US20190002369A1 (en) | 2019-01-03 |
KR20180034398A (ko) | 2018-04-04 |
US20190002767A1 (en) | 2019-01-03 |
EP3313568B1 (fr) | 2019-09-18 |
US10919820B2 (en) | 2021-02-16 |
EP3313568A1 (fr) | 2018-05-02 |
NL2015016B1 (en) | 2017-01-24 |
WO2016209074A1 (fr) | 2016-12-29 |
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